NO318680B1 - Method of preparing crystalline microporost metalloaluminophosphate from a solid body and use thereof - Google Patents

Description

The present invention relates to a method for producing metalloaluminophosphates (ELAPO), and more particularly for producing crystalline microporous silico-aluminophosphates (SAPO) of the molecular sieve type, from a solid body and also an application of this product as a catalyst for MTO production (conversion of methanol to olefins).

ELAPO is molecular sieve with a three-dimensional microporous network structure of tetrahedral AIO2, PO2 and EL02 units. In general, ELAPO has a chemical composition on an anhydrous basis which is expressed by the empirical formula:

where EL is either silicon, zinc, iron, cobalt, nickel, manganese, chromium or mixtures thereof, "x" is the mole fraction of EL and has a value of at least 0.005, "y" is the mole fraction of Al and has a value of at least 0.01, "z" is the mole fraction of P and has a value of at least 0.01, w is the mole fraction of H and x+y+z=l.

Silicoaluminum phosphates are a generic class of non-zeolitic molecular sieve materials that can be completely and reversibly dehydrated and yet maintain the same basic network topology in both the anhydrous and hydrated states.

One of these silicoaluminum phosphates, SAPO-34, is the most widely used catalyst for the MTO reaction. It has a chabasite structure (CHA) and is usually prepared from an alumina source, a silica source, a phosphorus source and at least one organic template. This template is usually tetraethylammonium hydroxide (TEAOH). A water dispersion of the gel formed when mixing the above components is hydrothermally treated at a temperature varying from 150 to 260 °C under autogenous pressure for

to crystallize SAPO-34. The material will also contain some water. The template is usually removed by heating the material in an oxygen-containing atmosphere (500-700 °C). The calcined material contains acidic protons and has catalytic properties.

If smaller amounts of Si are used during the synthesis with TEAOH as template, structures containing the AEI structure (US5609843) can be obtained. SAPO-5 (the AFI structure) can also crystallize from such gels. These structures are defined in Atlas of Zeolite Structure Types, W.M.Meier and D.H. Olson, Second Revised Edition 1987, from Butterworths.

US4861743 discloses a process for the production of a crystalline non-zeolitic molecular sieve in a preformed body or support. The crystalline non-zeolitic molecular sieve is made by bringing a liquid reaction mixture with spray-dried particles or extrudates of alumina or silica-alumina under hydrothermal conditions. The liquid reaction mixture contains a reactive source of phosphorus pentoxide and an organic templating agent. The crystallization takes place at high pressure and temperature and the preformed body reacts with the liquid mixture so that non-zeolitic molecular sieve is formed inside the body. Phosphorus can be an active component in the liquid or on the solid alumina or silica-alumina. Similarly, if the non-zeolitic molecular sieve contains silica, the reactive silica source can be included in the body and/or in the liquid reaction mixture. If the non-zeolitic molecular sieve is to contain one or more elements other than aluminium, silicon and phosphorus, the reactive sources for these elements can be included in the silica or silica-alumina body and/or in the reaction mixture. The minimum amount of water used in this method is 25 mol of water per moles of phosphorus. This means that only alumina or silica-alumina is used in the preformed body. All other reactive components are either impregnated on the body or in the liquid mixture. The described manufacturing method is liquid synthesis with excess liquid that must be removed afterwards.

US patent no. 5 514 362 describes the production of SAPO-5, SAPO-11, SAPO-31 and SAPO-39 from solid mixtures of alumina and silica gel, without removal of the excess liquid. The solid gel can be formed as self-supporting particles and the shape of the particles is preserved after crystallization. The gel includes alumina, silica, template and an active phosphorus source. In all the examples, the dense gel is extruded into the particles before the crystallization process. The molecular sieve crystallites formed are generally smaller than those usually formed in conventional processes.

European patent application no. 1 002 764 describes a method for producing small zeolite crystals inside a porous matrix with pores smaller than 1000 Å. This makes it possible to control the size of the zeolite crystals. The porous matrix can preferably be removed to isolate the pure zeolite or be useful as a component of the desired catalyst. Typical matrix materials are carbon or magnesium oxide, which represent the group of porous matrices that can be removed, and silica-alumina, which can be a desired component of the catalyst. To make the product, the matrix is impregnated with a synthesis gel which mostly consists of a zeolite precursor composition containing hydrated oxides of Si, Al and P, metal compounds and a zeolite template. The advantages of the method are to produce small crystallites and the porous matrix is used to control the crystal size. The porous matrix is not an active source for the crystallized zeolite.

US Patent No. 6,004,527 relates to a "dry" process for the preparation of a large molecular sieve by impregnating a solid cation oxide network structure with other reagents suitable for hydrothermal reaction between these reagents and the solid cation oxide network to create an impregnated pasta-free composition. The impregnated paste-free composition is then exposed to temperature and pressure conditions which produce a hydrothermal reaction and convert the reagents in the reaction into a crystalline molecular sieve which has the morphological properties of the solid cation oxide network. Examples of the production of zeolite particles from silica are described.

An aim of the present invention is to arrive at a cheap, simple and environmentally friendly production method for catalysts and absorbents of the metallo-aluminophosphate type (ELAPO). Production of silicoaluminophosphate (SAPO) is of particular interest. Another goal is to produce SAPO crystallites of suitable size and composition for the production of olefin from methanol. It is of particular interest to produce SAPO-34, SAPO-17 and SAPO-18, materials suitable for the methanol-to-olefins (MTO) reaction. A third aim is to show the general usability of the described production method in the production of SAPO-5, SAPO-11 and SAPO-20.

These and other objects of the invention are achieved by the method described below. The invention is further defined and characterized with the attached patent claims. The invention is further documented with reference to Figures 1-14, where: Figure 1 shows the RD (X-ray diffraction) pattern for the product from Example 1.

Figure 2 shows the RD patterns for the products fira Example 2 and 3.

Figure 3 shows the RD patterns for the products from Examples 4-8.

Figure 4 shows the RD pattern for the product from Example 9.

Figure 5A shows the RD patterns for the products from Examples 10-14.

Figure 5B shows the RD patterns for the products from Examples 15-19.

Figure 6 shows the RD patterns for the products from Examples 20-22.

Figure 7A shows the RD pattern for the product from Example 23.

Figure 7B shows crystallites of SAPO-34.

Figure 8 shows the RD patterns for the products from Example 24-25.

Figure 9 shows the RD patterns for the products from Examples 26-29.

Figure 10 shows the RD pattern for the products from Example 30.

Figure 11 shows the RD patterns for the products from Example 31-32.

Figure 12 shows the RD pattern for the product from Example 33.

Figure 13 shows the RD patterns for the product from Examples 34-36.

Figure 14 shows the RD patterns for the product from Example 37-38

The invention therefore relates to a method for producing crystalline microporous metalloaluminophosphate (ELAPO) from a solid body, where the body consists of particles containing Al and P. The pores in the particles are completely or partially filled by a liquid reaction mixture that includes an active source for EL the metal, an organic structure directing agent and water. The crystallization is carried out at high temperature under autogenous pressure to form crystals of microporous ELAPO, where the EL metal is either silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium or mixtures thereof. The EL metal can also be part of the solid body and in this case the liquid reaction mixture can be used with or without an active source for the EL metal. It is preferred to use silicon as the EL metal and produce crystalline, microporous SAPO. AlPO particles can be inside the body and they can also have an outer silica shell. It is preferred to use AlPO particles with a P/Al ratio of 1.2 - 0.6 and to carry out the synthesis in the absence of an external liquid. The particles can be calcined before treatment. The time for the hydrothermal reaction is 2-120 hours, preferably 4-20 hours. The crystallization should be carried out at temperatures from 150 to 260 °C, preferably 200 to 220 °C. As a structure-directing agent, one can choose either tetraethylammonium hydroxide (TEAOH), isopropylamine (IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine (CHA) or tetramethylammonium hydroxide (TMAOH). It is preferred to use reaction mixtures where the ratio between structure-directing agent and EL is 1-4. For the production of SAPO-18 and 34, it is preferred to use a TEAOH/Si ratio of 1-4. The ratio between the liquid volume and the pore volume (measured by liquid volumetric N2 adsorption) is 0.1-7, preferably 1-3. Surprisingly, it was also found that it was possible to prepare SAPO from a reaction mixture without stirring the reactants. It is preferred to produce SAPO-34, SAPO-17 and SAPO-18. SAPO-5, SAPO-11 and SAPO-20 can also be produced. The product can be used as an adsorbent or as a catalyst for the conversion of methanol into light olefins. The particles produced can also be used as catalysts for the production of olefins from an oxygen-containing feedstock containing at least one of the compounds methanol, ethanol, n-propanol, isopropanol, C4-C20 alcohols, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid or mixtures thereof.

The term "pores" here denotes all pores in the product, while "pore volume" is the volume measured by liquid volumetric N2 adsorption.

In contrast to previously known production methods, aluminum phosphate can be used here as an active source for both aluminum and phosphorus in the production of ELAPO. The aluminum phosphate is used in the form of porous particles. The AlPO particles can be precipitated in different ways, depending on which properties are desired.

For the production of SAPO, the preferred active silicon sources are silica sol or highly dispersed silica. Silica gel and silica hydrogel, silicates, silicic acid, colloidal silica, silica hydroxides, alkoxides of silicon and reactive solid precipitated silica will also be suitable. Silica can be reacted with the template solution beforehand, or it can be present as a physical mixture with the porous aluminum phosphate, or as a silicoaluminum phosphate.

An organic structure-directing agent is added to facilitate the crystallization of the molecular sieve. A mixture of two or more structure-directing agents can also be used. Suitable structure-directing agents include tetraethylammonium hydroxide (TEAOH), isopropylamine (IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine (CHA) and tetramethylammonium hydroxide (TMAOH).

To make SAPO, porous AlPO particles are mixed with a small amount of water, a silicon source and a solution containing a structure directing agent to saturate the pores of the particles. The water content is so small that the mixture appears dry, which is why the term "dry synthesis" is used. Another term for this technique is "incipient wetness". Alternatively, the Si source can be present as a separate phase of the solid AlPO or as a silicoaluminum phosphate mixture. Slightly different mixing procedures can be used in the preparation of the reaction mixture, for example by changing the order in which the liquids and A1PO are added. Preferably, the mixing of the reactants is carried out by a dry synthesis technique and gives a liquid volume to pore volume ratio of approximately between 0.1 and 7 , preferably 1 to 4 and preferably 1 to 3. The reaction mixture is placed in a tight pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene. The reaction mixture is heated under autogenous pressure at a temperature in the range 150 °C to 260 °C, preferably 200 to 220 °C for a period of from a few hours to a few days, typically 2-120 hours, preferably about 4-20 hours. The crystallization occurs in the absence of a continuous liquid phase. The idea is that seeds for one or more SAPOs (e.g. SAPO-34/ SAPO-18/ SAPO-5) are formed inside the pores of the carrier paticle. The manufactured product is calcined at 500-600 °C for a few hours in dry air to remove the organic structure directing agent from the pores of the crystalline material. The resulting molecular sieve has a three-dimensional microporous crystal network with a SAPO micropore structure.

After the SAPO synthesis, particles can be produced from a mixture of the crystallized material and a suitable binder (e.g. fluid bed particles).

Materials suitable for use in fluidized bed reactors are typically made by spray drying a slurry of the active catalyst. Other materials are often added to the sludge to adjust the physical properties and mechanical strength of the finished particle.

When SAPO-34 is produced by "dry synthesis" from a porous AIPO4 mixed with a silica source and template/water, the following substitution will be obtained:

where n >1.

This corresponds to using 1 mol of base/Si and up to 3 mol of base to neutralize the phosphoric acid. Since it is probably not necessary to completely neutralize the phosphoric acid (3 mol of base), only 1-2 mol of base may be sufficient for this neutralization.

This may indicate that an A1PO with a P/Al ratio of approximately 0.8 (1.2-0.6) is better suited than an A1PO with P/Al = 1. An advantage of using such an A1PO is that the amount of template required for a synthesis, or to make additional addition of base unnecessary, is reduced to a minimum.

It will also (if you use A1PO with P/A1=1) unnecessary to use the more expensive template, TEAOH, as a neutralizing agent. For example, isopropylamine (IPA) can be used. In other words, a significant proportion of the template TEAOH can be replaced with IPA to make the synthesis more cost-effective.

The present synthesis method has the following advantages compared to known methods: A. Use of porous A1P0 as a precursor for the microporous crystalline silicoaluminophosphate makes it possible to use significantly smaller amounts of organic template, besides making it possible to use cheaper amines as part of a template mix.

B. Because less water is used (unlike H20/A1=25 in US4861743 and H20/A1=17.5 - 22.5 in US6207872 and H20/A1=15 in Lok et al. US Patent 4440871 (Example 25) , H20/A1 is mostly 5-10 in this invention) during the hydrothermal synthesis than in the known methods, it is unnecessary to filter and wash the product and no polluted water is produced that needs to be purified. C. The intimate mixture of liquid and solid that is formed when the pores of the solid are filled with the synthesis liquid makes it unnecessary to stir the synthesis mixture. This makes it possible to use simpler autoclaves for the hydrothermal synthesis step. D. The intimate contact between solid and liquid also results in faster nucleation and a higher crystallization rate, which leads to shorter reaction times and to the size of the crystallites being 0.2-1 pm, compared to 0.5-3 | Jm for a SAPO-34 prepared according to the method in Lok et al. in US patent 4440871. The smaller particles provide an MTO catalyst with a longer shelf life and an expected higher adsorption rate. By using small amounts of Si and template, it is possible to achieve only partial conversion of the porous solid into crystalline material.

Examples

The invention is further illustrated by means of the following examples.

A description with properties of the different AlPO materials used in the present invention is presented in Table 1. The porosity in the materials was characterized by adsorption of liquid N2 and the elemental composition by X-ray fluorescence analysis.

Production of the aluminum phosphates used

The manufactured aluminum phosphate powders mentioned in Table 1 were made according to the method in US4364855. The resulting gels were washed and filtered to remove NH 4 NO 3 and then dried at 100 °C and calcined in an oven at 400 °C for 16 h. The spray-dried samples were produced from an aqueous slurry in a conventional spray dryer. The material designated by K00-092.004 was spray-dried from a slurry with added Ludox LS30 so that there was 20 weight percent Si02 in the finished particle.

If not mentioned otherwise in the text, a Teflon-lined autoclave with a volume of 40 ml and a synthesis temperature of 210 °C was used. A detailed overview of all the syntheses presented in this invention is listed in Table 2.

The following reagents were used unless otherwise stated:

Silica source: Ludox LS30; 30% by weight suspension in water (pH = 8.2), Du Pont product.

TEAOH (tetraethylammonium hydroxide; Aldrich; 35% by weight)

IPA (isopropylamine; Fluka; 99.5% by weight)

DPA (diisopropylamine; Fluka; 99 wt%)

Tripropylamine (Fluka, 98% by weight)

The TMAOH (tetramethylammonium hydroxide pentahydrate; Fluka, 9 wt%) AlPO materials in this invention are listed in Table 1.

RD analysis

The products are analyzed with an X-ray powder diffractometer, Siemens D-5000, which provides monochrome radiation (from a CuKc source) with wavelength equal to 1.54056 Å. Most of the RD patterns presented in this invention are shown together with the RD pattern of a SAPO-34 reference which was prepared by a conventional wet synthesis substantially similar to that disclosed in US4440871 (B.M. Lok et al., Example 35). The diffraction pattern of this latter reference sample is denoted "RUW" in the figures.

Example 1

Production of SAPO-34 from AlPO particles (EWH8-16)

A synthesis mixture was made by first adding 2.0 g of Ludox LS30 to 8.0 g of a porous AlPO material (K00-102.003, Table 1) and then adding 14.0 g of 35% TEAOH and 5.0 g of water under thorough stirring. To the water was added 0.35 g of HCl prior to mixing. The mixture was reacted in a Teflon-lined stainless steel autoclave at 210°C for 72 hours. The RD pattern of the resulting silicoaluminophosphate product is shown in Figure 1 (EWH8-16) and confirms that an almost pure SAPO-34 has been formed. The reflection at about 26 degrees is believed to represent a dense AlPO4 phase.

Example 2

Partial removal of water before hydrothermal treatment (EWH8-10)

In this synthesis, 5.0 g AlPO-Iett (Table 1) was used as the AlPO source and mixed with 3.1 g Ludox LS30, 8.8 g TEAOH and 3.1 g water using the mixing procedure outlined in Example 2 .

The mixture was heated in an oven at 97 °C until the liquid mass was reduced from 15.0 g to 6.2 g, which corresponds to a loss of 8.8 g of water by evaporation, or about 80% of the total water content of the original sample. The mixture was reacted in a Teflon-lined stainless steel autoclave at 210 °C for 42 hours, and the RD pattern in Figure 2 confirms that SAPO-34 was formed.

Example 3

Partial removal of water before hydrothermal treatment ( EWH8-11)

This synthesis is identical to the synthesis in Example 2, except that slightly less water was allowed to evaporate, approximately 40% by weight of the total water content of the original sample. The RD pattern in Figure 2 confirms that SAPO-34 was formed.

Example 4-8

Production of SAPO-34 from different A1PO (EWH11-6, 12-4, 15-8, 16-7, 17-8) Five different A1PO with the designations K00-053.001 were tested. K00-058.001, K00-077.008, K00-102.003 and K00-092.004 (see Table 1). In contrast to the previous synthesis (Examples 1-3), only 2.0 g of A1PO was used in each of the present examples. Also, the "free" volume or available "gas volume" in the Teflon-lined autoclave was reduced from about 40 mL to 3-5 mL by inserting a compact, cylindrical Teflon insert into the Teflon-lined autoclave. The reduction of this "free" volume was done to limit the amount of water in the vapor phase.

A mixing procedure was also used that was slightly different from that described in Examples 2 - 3, when Ludox LS30 (respectively 0.26 g, 0.85 g, 1.18 g, 1.52 g, 0.12 g ), was mixed together with the organic template TEAOH (1.86 g, 1.78 g, 2.48 g, 3.2 g, 2.6 g, respectively), and the resulting solution was added to the AlPO powder with dry -synthesis by thorough mixing.

The mixtures were reacted in Teflon-lined stainless steel autoclaves at 210 °C for 20 hours. The RD patterns of the crystalline products (Figure 3) are all consistent with the formation of SAPO-34. The many other intense diffraction lines that appear in the RD pattern of sample EWH11-6 originate from aluminum ammonium hydroxide phosphate.

Example 9

Preparation of SAPO-34 in the absence of Ludox (EWH17-4)

The surface of one of the AlPO materials (KOO-092.004; Table 1) contained a silica shell that had been formed by spray drying. The silica content was approximately 20 percent by weight. To 2.0 g of the AlPO material, 2.7 g of TEAOH were added by dry synthesis with thorough mixing. The mixture was reacted in a Teflon-lined stainless steel autoclave at 210°C for 20 hours. The RD pattern of the resulting crystalline powders showed that pure SAPO-34 had been formed (Figure 4).

Example 10 - 19

Mixture of two organic structure-directing agents in a reaction mixture

(ABA135-1-5/ 136-1-5)

In the following examples, two different methods were used for the syntheses: a) the Si content and the molar ratio TEAOH/Si were kept constant and the molar ratio IPA/Si varied and b) the Si content and the molar ratio IPA/Si were kept constant and the molar ratio TEAOH/ Say varied. Table 2 shows the actual amount of reactants used. The A1PO used in these syntheses was K00-218.002 (Table 1). In these examples, Ludox, the organic template(s) were mixed together and then water was added by dry synthesis under thorough mixing.

As in Examples 4-8, the available "free" volume in the Teflon-lined autoclave was reduced from approximately 40 ml to only 3-5 ml by inserting a compact, cylindrical Teflon insert into the Teflon-lined autoclave. The mixtures were reacted in Teflon-lined stainless steel autoclaves at 210 °C for 20 hours.

As the RD pattern of the crystalline products suggests (Figure 5A and B), SAPO-34 is formed in all the syntheses, except AB A-136-1, where only isopropylamine (IPA) was used as an organic additive.

Two of the products produced, ABA-135-5 and ABA-136-2, appear to consist of largely pure SAPO-34. Both of these samples had - before the synthesis - the same molar ratio of 2.0 between IPA and TEAOH. However, sample ABA-135-5 contained twice as much template as sample ABA-136-2.

The RD pattern for most of the products shows that a small amount of A1PO-18 or SAPO-18 is formed, which - tentatively - can be read by the appearance of the diffraction line 20 = 17.0°. As can be concluded from the data in Figure 5, the relative amount of A1PO/SAPO-18 depends on the relative concentration of reactants (Table 2) in the synthesis mixture.

Example 20 - 22

Mixing of templates in the absence of Ludox (EWH18- 1, 2 and 4)

With largely the same procedure as in Examples 10 - 19 and with K00-092.004 instead of A1PO (Table 1), three reaction mixtures without Ludox were made. The composition of the reaction mixture is summarized in Table 2. The mixtures were reacted in Teflon-lined stainless steel autoclaves at 210 °C for 20 hours.

The RD pattern of the resulting crystalline powders showed that SAPO-34 was formed (Figure 6). However, if the relative amount of IPA was increased while the total amount of organic additives (TEAOH and IPA) was constant (Table 2), small amounts of some other crystalline substances were also formed.

Example 23

Scaling up ( ABA127)

An attempt to scale up the synthesis of SAPO-34 was begun by increasing the amounts of all reactants by a factor of 30 compared to Example 10. The smaller Teflon autoclave (40 mL) was replaced with a larger one of approximately 200 mL. A total of five identical portions were made, with 60 g of the AlPO material K00-218.002 in each (Table 1), 16.4 g of Ludox LS30 and 69.1 g of TEAOH. The reactants were mixed as described in Examples 4-8. The total liquid volume was approximately twice the available pore volume in the porous AlPO material.

The RD pattern of the resulting crystalline powders mostly showed only SAPO-34 (Figure 7A). It appears that a small amount of A1PO-18/SAPO-18 is formed, which is tentatively concluded from the observed diffraction line at 20 = 17.0°. The RD of only one of the replicates is shown in Figure 7A, simply because of the excellent reproducibility observed for the five portions.

The size of the regularly shaped SAPO crystallites is typically in the range 0.25 to 1 µm, as can be seen from Figure 7B.

Example 24 - 25

No stirring of reactants prior to the hydration treatment. (ABAl 39- 3 and 4)

2.0 g of an AlPO material KOO-218.002 (see Table 1) was mixed with 0.55 g of Ludox LS30 together with 2.3 g of an organic additive (TEAOH). Water was then added by dry synthesis with thorough mixing (ABA139-3). Another and identical AlPO material was added to the same type and amount of liquid reactants, without stirring

(ABA139-4). See Table 2 for more information. Both mixtures were reacted in Teflon-lined stainless steel autoclaves at 210 °C for 20 hours.

As can be confirmed from the RD patterns (Figure 8), the two crystalline products were identical. Moreover, the intensities (areas) of the corresponding diffraction lines for the two samples were identical, which suggests that stirring or not stirring the reactants before the hydrothermal treatment is of little importance for the product distribution after the hydrothermal treatment. The results suggest that stirring is not a critical factor, so that no special precautions need to be taken during production, thus saving costs.

Examples 26 - 29

Effect of water in the reaction mixture (ABA140- 1, 2, 3 and 4)

Four AlPO powder samples, each 2.0 g, (K00-218.002; Table 1) were mixed with 2.3 g 35% TEAOH, 0.55 g Ludox LS30 and water following the same mixing procedure outlined under Example 24. The difference between the reaction mixtures used in the present examples and the corresponding reaction mixture in Example 25 was the proportion of water used (Table 2). The water content was varied by 0, 0.5, 1.0 and 3.0 in the different mixtures. The mixtures were reacted in Teflon-lined stainless steel autoclaves at 210 °C for 20 hours.

As could be confirmed from the RD patterns in Figure 9, the resulting products were identical. Moreover, the intensities (areas) of the different diffraction lines for the four samples were identical, suggesting that the addition of "external" water has no significant effect on the product distribution. This result is probably not very surprising, since most of the reactants contain some "intrinsic" water, i.e., water present in the actual chemical reactants used in the present synthesis (eg 35% TEAOH and Ludox LS-30).

Example 30

Preparation of SAPO-5 (ABA143-4)

2.0 g of an AIPO "KOO-058.001" powder sample (Table 1) was mixed with 0.78 g of tripropylamine, 0.55 g of Ludox LS30 and 3.0 g of water. The mixing and crystallization procedures were the same as in Example 24.

The RD pattern reference for SAPO-5 (Figure 11; see "collection of simulated XRD powder patterns for zeolites", third revised edition, M.MJ.Treacy, J.B.Higgins and R. von Ballmoos, 1996) shows that a significant amount is formed SAPO-5 by the above synthesis reaction. But the SAPO-5 that is formed is not pure.

Example 31 ■ 32

Production of SAPO-20 (ABA145-4, ABA-I45-2)

The same type of AlPO powder as in Example 31 ("KOO-058.001"; Table 1) was mixed with tetramethylammonium hydroxide pentahydrate, Ludox LS30 and water with the same mixing and crystallization procedure as in Example 24. Two synthesis reactions were started. The amounts of reagents used are shown in Table 2.

The RD pattern reference for SAPO-20 (Figure 11; see "collection of simulated XRD powder patterns for zeolites", third revised edition, M.MJ.Treacy, J.B.Higgins and R.

von Ballmoos, 1996) shows that pure SAPO-20 can be formed by the above synthesis reaction if one chooses a suitable concentration region for the chemical reactants.

Example 33

Preparation of SAPO-11 (ABA144-2)

The same type of AlPO powder (2.0 g) as in Example 31 ("KOO-058.001"; Table 1) was mixed with diisopropylamine (0.37 g), Ludox LS30 (0.55 g) and water (3.2 g) following the same mixing and crystallization procedure as in Example 24.

The RD pattern reference for SAPO-11 in Figure 12 (see "collection of simulated XRD powder patterns for zeolites", third revised edition, M.MJ.Treacy, J.B.Higgins and R.

von Ballmoos, 1996) confirms that pure SAPO-11 can be formed by the above-mentioned synthesis reaction if one chooses a suitable concentration region for the chemical reactants.

Example 34-36

Variation of the time for the hydrothermal treatment (ABA146-1,2 and 3)

Three products were prepared according to the synthesis recipe outlined in Example 10 and with the same porous A1PO (K00-218.002, Table 1). Only the synthesis time was varied (from 20 hours to 8 hours to 4 hours, Table 2). RD patterns for the respective products are illustrated in Figure 13 and they show that SAPO-34 is formed after a fairly short hydrothermal treatment, less than or equal to 4 hours. These results suggest that the crystallization time can be significantly reduced without loss of product quality, which will save production costs.

Example 37-38

Synthesis of SAPO-34 with a low amount of template (ABA147-2, ABA151-3)

The production is carried out according to the mixing procedure described in Examples 1-3 and with the autoclave type with Teflon insert described under Examples 4-8. AlPO (KOO-058.001) was added to Ludox LS-30 and then TEAOH and water with thorough mixing. The synthesis temperature was 210 °C for 20 hours. The RD patterns for the different products are illustrated in Figure 14. From these RD patterns we clearly see that SAPO-34 is formed despite the low amount of template.

Example 39

MTO characteristics in a fixed bed reactor

Catalytic testing

Catalytic tests were carried out for the conversion of methanol to light olefins. The sample of the calcined material to be tested was compressed into tablets, which were then carefully crushed. A 35 - 70 mesh fraction was removed by sieving. 1.0 g of the powder was placed in a quartz reactor and heated to 400 °C in N2 and held at this temperature for 30 minutes, before the temperature was increased to 420 °C and a mixture of 40% methanol and 60% nitrogen was passed through it with a WHSV = 1 g MeOH/g cat/h. The products were analyzed by gas chromatography. The lifetime of the catalyst was defined as the time for breakthrough of dimethyl ether on the stream (t-DME defined as the time when the carbon selectivity of dimethyl ether (DME) on the stream in the waste stream was < 1%).

The C-based product selectivity of the tested samples is presented in Table 3. The results indicate that the SAPO-34 materials made from solid, porous A1PO materials with dry synthesis are good catalysts for the conversion of methanol to light olefins.

In Table 3 we have listed the catalytic results that appeared on a limited selection of the samples from Table 2. The catalytic test conditions are shown in the text. As a reference sample, a SAPO-34 sample from a "traditional" wet synthesis (US 4440871, B.M. Lok et al., Union Carbide 1984) was used.

Example 40

MTO characteristics in a fluidized bed reactor

A slurry was made of the material from Example 23, the aluminum phosphate K00-218.002 (Table 1) and SiO2 (Ludox HS40). The slurry was spray dried in a conventional spray dryer with the outlet temperature set at approximately 100°C. The material was then calcined in an oven at 550 °C for 8-16 hours, and the finished material is called a prototype catalyst. Elemental analysis of the material indicated 35% by weight SAPO-34.

The material was tested in a table-scale fluidized bed reactor with online GC analysis. The results were compared with a generic SAPO-34-based catalyst from UOP (id 07045-16) at identical WHSV based on SAPO-34. The lifetime of the catalyst defined as the time for breakthrough of dimethyl ether on the stream and the product selectivity are shown in Table 4.

The examples show use of the catalyst in the production of light olefins from methanol.

Claims (21)

1. Method for producing crystalline microporous metalloaluminophosphate (ELAPO) from a solid body, where the body consists of particles containing mainly aluminum phosphate and where the pores of the particles are completely or partially filled with a liquid reaction mixture that includes an active source for the EL metal, an organic structure-directing agent and water, and where the crystallization is carried out at high temperature under autogenous pressure so that crystals of microporous ELAPO are formed, where the EL metal is either silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium or a mixture of these. 2. Method for producing crystalline microporous metalloaluminophosphate (ELAPO) from a solid body, where the body consists of particles containing mainly the EL metal and aluminum phosphate, where the pores of the particles are completely or partially filled with a liquid reaction mixture that includes an organic structure-directing agent and water, and where the crystallization is carried out at high temperature under autogenous pressure so that crystals of microporous ELAPO are formed, where the EL metal is either silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium or a mixture of these. 3. Method according to claim 1 or 2, where the EL metal is silicon and where crystalline microporous SAPO is produced. 4. A method according to claim 1 or 2, wherein AlPO particles with a P/Al ratio of 1.2-0.6 are used. 5. A method according to claim 2, wherein the liquid reaction mixture also contains an active source for a metal EL. 6. A method according to claim 5, wherein the metal is silicon. 7. A method according to claim 1 or 2, wherein AlPO particles with an outer silica shell are used. 8. A method according to claim 1 or 2, wherein the synthesis is carried out without an external liquid. 9. Method according to claim 1 or 2, where the crystallization is carried out at a temperature of between 150 and 260 °C, preferably 200-220 °C. 10. Method according to claim 1 or 2, where the time for the hydrothermal reaction is 2-120 hours, preferably 4-20 hours. 11. Method according to claim 1 or 2, where the particles are calcined before the treatment. 12. Method according to claim 1 or 2, where the ratio between the liquid volume and the pore volume is 0.1-7, preferably 1-3. 13. Method according to claim 1, 2 or 3, where the molecular sieve is SAPO-34, SAPO-17 or SAPO-18. 14. Method according to claim 1, 2 or 3, where the molecular sieve is SAPO-5, SAPO-11 or SAPO-20. 15. Method according to claim 1, 2 or 3, where the structure-directing agent is one or more of the organic structure-directing agents tetraethylammonium hydroxide (TEAOH), isopropylamine (IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine (CHA) and tetramethylammonium hydroxide (TMAOH). 16. Method according to claim 1, where the ratio between structure directing agent and EL is 1-4. 17. Method according to claims 3 and 15, where the ratio TEAOH/Si is 1-4. 18. A method according to any one of claims 1-17, wherein ELAPO is prepared from a reaction mixture without stirring the reactants. 19. Use of crystalline microporous metalloaluminophosphate as prepared according to claims 1-18 as an adsorbent. 20. Use of crystalline microporous metalloaluminophosphate as prepared according to claims 1-18 as a catalyst. 21. Use of crystalline microporous metalloaluminophosphate as prepared according to claims 1-18 in a catalyst for the production of olefins from an oxygen-containing raw material that includes at least one of the compounds methanol, ethanol, n-propanol, isopropanol, C4-C20 alcohols, methyl ethyl ether , dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid or mixtures thereof.